Production of unsaturated nitriles



Patented Dec. 10, 1946 I I UNITED STATES PATENT OFFICE 2,412,437 I PRODUCTION OF UNSATURATED NITRILES Cary R. Wagnen'Uti ca, Ohio, assignor to Phillips Petroleum Company, a corporation of Delaware 'No Drawing. Application November 29, 1943, Serial No. 512,255

3 Claims. (Cl. 260-464) 1 2 This invention relates to the manufacture of The saturated aldehyde has the general formula unsaturated aliphatic nitriles, More specifically CnH2n+1 CHO and the unsaturated aldehyde has it is concerned with the production of acrylonithe general formula CnH2n-1CHO, where n has trile and its homologues from saturated or unthe same significance as before. The number in saturated aldehydes and ammonia. 5 is at least 2 and is usually not greater than 6.

It is well known that the reaction between am- The reactions are:

monia and an aldehyde at'ordinary low temperatures produces an addition product called an (1) r CnH2n-1 CN+H2O+2H2 aldehyde ammonia. The formation of these and products from the lower molecular weight alde- I hydes is reported extensively in the literature. (2) C'ZHMA cHo+NHsacnHzfld CN+H2O+H2 It has also been reported (Mailhe and deGodon, In carryingout the process of my invention, I Compt. rend, 166, pp. 215-216, 1918) that satupass a mixture of aldehyde vapors and gaseous rated nitriles may be produced by passing a ammonia, with Or without an inert diluent,

mixture of aldehyde pors and ammonia over through a catalyst chamber containing a dehya dehydrating catalyst at 420-440 C. So far as drating-dehydrogenating catalyst at a tempera- I am aware, however, no one has heretofore sucture in the dehydrogenation range and most deceeded in obtaining good yields of unsaturated sirably in the range of 900 to 1300 F. and under nitriles by a reaction between the corresponding a pressure differential sufiicient to force the realdehyde and ammonia. actants through the system at the desired rate. I am aware that it has been proposed to form The effiuents from the catalyst chamber are unsaturated nitriles by dehydrogenation of the cooled quickly, for example, by means of a water corresponding saturated nitrile. French Patent quench, and are then conducted to a fractiona- 790,262, to I, G. Farbenindustrie, issued Novemtion system for separation of the desired product. ber 1 1 disclos s th catalytic dehydrogena- Unchanged reactants and insufiiciently dehydrotion of low molecular weight saturated nitriles genated products may be recycled to the catalyst (e. g. propionitrile and isobutyronitrile) at temch mber, peratures of the order of 700 C. with the forma The reactants may be introduced into the catti n f s atu d nitriles Also, the alyst chamber separately, but I prefer to mix the thermal decomposition of prop trile in a silica so two vapor streams before they reach the reaction tube at 675 C. has been reported to yield a small zone. Proportions of the two reactants may be amount of acrylonitrile (Rabinovitch and Winkvaried over wide limits but in general an excess ler, Canadian Journal of Research, 20, B69, 1942). of ammonia in the catalyst chamber is'preferred.

It is an object of my invention to provide a v By excess" I mean a stoichiometric excess over continuous process for the manufacture of low the aldehyde. The molar ratio of ammonia to molecular weight unsaturated nitriles by the realdehyde may range as high as 5 to 1. An inert action of an aldehyde with ammonia. A further diluent such as nitrogen gas may be added if object is to provide a process in which the dedesired. It is preferred that the reactants be sired reaction is accomplished in a single step. anhydrous or substantially anhydrous.

I have now found that unsaturated aliphatic 40 A large number of catalytic substances are nitriles may be produced in good yields by passsuitable for use in my process, the main requireing a mixture of the corresponding aliphatic ments being that they promote both dehydrogenaldehyde and ammonia over a dehydrating-deation and dehydration reactions at temperatures hydrogenating catalyst under conditions such within the dehydrogenation range. In general, that the principal product of the reaction is an compounds, especially the oxides and sulfides, of

, unsaturated nitrile having the same number of the metals of groups 2-7 of the periodic system carbon atoms as the original aldehyde. Thus, of the elements, such as the oxides or sulfides of for example, I may produce acrylonitrile from magnesium, zinc, aluminum, titanium, vanadium, propionaldehyde, or alpha methylacrylonitrile molybdenum, zirconium, chromium, manganese from isobutyraldehyde. It is within the scope of and thorium are satisfactory. They may be used my invention to employ as a starting material either singly or in admixture with one or more either a saturated aldehyde or an unsaturated other catalytic substances, and if desired may aldehyde such as acrolein. In the latter case the be deposited on supporting materials such as sildehydrogr nation conditions in the reaction 'zone ica gel, pumice, pipe clay, Activated Alumina and may besomewhat less severe since the desired the like, A particularly advantageous catalyst unsaturation in the carbon chain is already presis composed of a minor proportion of chromium ent. The process is applicable to the production sesquioxide, CrzOa, deposited on Activated Alumiof unsaturated nitriles generally and particularly na, such as is described in U. S. Patent 2,172,540. to those having the general formula CnH2n1CN, In general I prefer to use difficultly reducible oxwhere n is a small whole number greater than 1. ides of the metals of groups 2-'? of the periodic mixtures of chromium oxide and aluminum oxide, zinc oxide and aluminum oxide, etc.

Any convenient arrangement for contacting the reactant vapors with the catalyst may be employed. The catalyst may be deposited in fixed beds and heated by circulating fluids in pipes buried in the catalyst mass, it may be placed in metal tubes arranged so as to be heated externally by hot gases, or it may be finely divided and contacted with the reactants in a fluid state.

It is also possible to carry out my process in the absence of catalysts, by passing the reactants under reduced pressure through an open tube made of some suitable refractory material such as silica and heated to a temperature in the dehydrogenation range and preferably in the higher portion thereof namely 1200 to 1300 F. Longer contact times are required than when catalysts are used, however, and the yield of the desired unsaturatednitrile is lower; therefore, catalytic treatment is preferred.

The pressure in the catalyst chamber may be varied over a rather wide range from well below atmospheric to as high as 6 or 8 atmospheres, or even higher, but it is desirable to maintain a low partial pressure of the aldehyde vapors and of the resulting nitrile. This may be accomplished either by operating at a low over-all pressure or by adding an inert diluent. An excess of ammonia also serves the same purpose and if provision is made for recovery and recycling of unchanged ammonia a. suitable excess of that gas may be maintained in the reaction zone without an uneconomical Waste of raw material. A sufficient pressure differential must, of course, be maintained to cause the reactants to pass through the reaction zone at a satisfactory flow rate. This should be adjusted so as to give a contact time sufiicient for an economical conversion per pass but not so long as to result in an excessive amount of decomposition or polymerization of the product. In any given case the optimum contact time will be found to depend upon the reaction temperature and the activity of the catalyst employed. In general a contact time of less than seconds is satisfactory, and it is preferred to employ a contact time of less than 2 seconds 4 for the production of acrylonitrile and its homologues. By using short contact times and recycling unchanged reactants and insufiiciently dehydrogenated products it is possible to avoid excessive decomposition and polymerization and yet obtain good ultimate yields.

Rapid cooling of the efiiuents from the reaction zone is quite advantageous in that decomposition and polymerization are thereby minimized. This cooling may be accomplished in any conventional manner, but I prefer using a direct water quench. Separation of the product and the recycle materials is then readily accomplished, for-example, by fractional distillation.

In the steps of separation and further purification of the unsaturated nitriles it is desirable to use a polymerization inhibitor selected from those substances which are known to the art, for example, chromium methacrylate.

The practice of my invention may be better understood by a reference to the following examples, which are not intended to limit the scope of the invention.

Example 1 A mixture of propionaldehyde vapors and ammonia gas, in a mol ratio of 1:2, was passed through a catalyst chamber containing chromium sesquioxide (30% by weight) deposited on Activated Alumina (70% by weight). The catalyst chamber was maintained at a temperature of 1100 F. and the pressure therein was approximately 5 lbs. per square inch gage. The reactants were passed through the catalyst chamber at a rate of. about 1800 volumes per volume of catalyst per hour, equivalent to a contact time of approximately 1 second. The efiluents from the catalyst chamber were quenched to room temperature by means of a spray of cold water, and the products separated by fractional distillation. Acrylonitrile, B. P. 78 C. was recovered in good yield.

Example 2 Isobutyraldehyde vapors were mixed with ammonia gas and passed through the catalyst chamber under the same conditions as those set forth in Example 1. Twenty per cent by volume of nitrogen gas was added to the reactants as an inert diluent. The eflluent was quenched as in Example 1 and the products separated by fractional distillation. Alpha-methylacrylonitrile, B. P. 92 C. was obtained.

Example 3 The vapors of acrolein were mixed with anhydrous ammonia gas in a mol. ratio of 1:2 and the mixture was passed over the catalyst of Example 1 at a temperature of 950 F. and a pressure of approximately 5 lbs. per square inch gage. The contact time was 0.5 second. The efliuent was quenched as in Example 1 and theproducts separated by fractional distillation. Acrylonitrile was obtained in good yield.

I claim:

1. The process of making acrylonitrile which comprises subjecting a mixture of propionaldehyde and ammonia to the action of chromium sesquioxide deposited on alumina as acatalyst at a temperature of from 900 to 1300 F. and for a contact time of less than 2 seconds and thereby forming acrylonitrile as the principal product of the reaction.

2. The process of making acrylonitrile which comprises subjecting-a mixture of acrolein and ammonia to the action of chromium sesquioxide deposited on alumina at a temperature of from 900 to 1300 F. and for a contact time of less than 2 seconds.

3. A process for the preparation of an unsaturated aliphatic nitrile having the general formula CnH2n-1CN where n is a small whole number greater than 1 and not greater than 6 which comprises passing a mixture of ammonia and an aliphatic aldehyde having the same number of carbon atoms as the nitrile to be produced into contact with chromium sesquioxide deppsited on alumina at a temperature within the range of from 900 to 1300 F. for a contact time of less than 5 seconds.

CARY R. WAGNER. 

